Calcium-sodium polysulfide chemical reagent and production methods

ABSTRACT

A calcium-sodium polysulfide chemical reagent and methods for producing the reagent. The reagent is a blend of calcium polysulfide and sodium polysulfide that can be prepared using various types, sources and ratios of lime, elemental sulfur and sulfide ion using either virgin or waste materials. The reagent is amenable to inexpensive and high rate production methods at ambient or warmer temperatures. The reagent can be used to precipitate metals from wastewater, stabilize hexavalent chrome in hazardous waste residues, remove mercury from coal fired power plants, and as an electrolyte in large-scale bromide/polysulfide electrical storage batteries.

RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 11/106,330, filed Apr. 14, 2005 now U.S. Pat. No. 7,534,413which is a continuation-in-part of U.S. patent application Ser. No.10/977,826, filed Oct. 29, 2004 now U.S. Pat. No. 7,144,362, the entiredisclosures of each of these applications are hereby expresslyincorporated by reference, and priority to each of these applications isclaimed under 35 U.S.C. §120.

TECHNICAL FIELD

The present invention relates to polysulfide reagents that areparticularly useful for precipitating metals from wastewater,stabilization of multivalent metals such as chrome in hazardous wasteresidues, mercury removal from flue gases, and as an electrolyte inlarge-scale bromide/polysulfide electrical storage batteries. Thepresent invention is further directed to methods to produce thepolysulfide reagents.

BACKGROUND ART

It has become increasingly apparent over the past few years that severalnew technologies are emerging that will require large quantities ofinexpensive alkaline polysulfide chemical reagents. One such technologyhas focused on the stabilization of the massive amounts of chromite oreprocessing residues (COPR) that have accumulated at various sitesthroughout the United States over the last several decades due to theabsence of a cost-effective treatment methodology.

According to one application of alkaline polysulfide chemical reagentswhich is disclosed in U.S. Pat. No. 6,214,304 to Rosenthal, it has beenfound that injecting alkaline polysulfides into the flue gas ofcoal-fired power plants can be highly effective for enhanced removal ofmercury.

Another important area of emerging technologies involves regenerativefuel cells such as described in U.S. Pat. No. 6,841,294 to Morrissey.This area of technology, which is receiving ever increasing attention,requires large amounts of polysulfide reagents that are used aselectrolytes in storage batteries.

Calcium polysulfide and sodium polysulfide are generally designated asCaS_(x) and Na₂S_(x), respectively, where x indicates the number ofsulfur atoms. Although many different methods for making calciumpolysulfide or sodium polysulfide reagents have been previouslydeveloped over a period of many years, such methods are typicallydirected to making one type of polysulfide or the other, but not both ormultiple types simultaneously.

U.S. Pat. No. 1,434,266 to Taki is directed to a method for themanufacture of lime sulphur in which a mixture of calcium oxide (quicklime), elemental sulfur and water is steam heated above the meltingpoint of sulfur in a pressurized revolving reactor to make a “limesulfur” solution containing calcium polysulfide.

A similar method using a different type of reactor is disclosed in U.S.Pat. No. 4,624,419 to Hevesi et al. which is directed to an apparatusfor preparing aqueous and oily sulfur containing products.

The chemical reaction for such methods is essentially:3Ca(OH)₂+(2x+2)S^(o)+heat→3H₂O+CaS₂O₃+2CaS_(x)  (1)

Similar reactions can be written in which the hydrated lime, Ca(OH)₂, isreplaced with quick lime, CaO; and the calcium thiosulfate, CaS₂O₃, isreplaced by calcium sulfite, CaSO₃.

Work by others lead to the accepted conclusion that methods based on theabove reaction are undesirable because: (1) they require hightemperatures (near boiling) to enable part of the elemental sulfur to bereduced to the sulfide ion needed for forming polysulfide; (2) theequivalent amount of elemental sulfur that is oxidized to thiosulfateion (or alternatively to sulfite ion) to complete theoxidation-reduction reaction causes the polysulfide yield to be low; (3)the resulting product liquor is not a mixture of polysulfides alone; and(4) the thiosulfates and sulfites generate a great deal of sludge solidsthat limit the concentration at which the product can be produced.

U.S. Pat. No. 1,517,522 to Volck discloses a process for producing limesulphur compounds. Volck teaches that a preferable method for makingcalcium polysulfide involves adding hydrogen sulfide to the lime-sulfurreaction to eliminate the consumption of elemental sulfur needed forinternal generation of the sulfide. The reaction for calciumpentasulfide occurs as follows:Ca(OH)₂+H₂S+4S^(o)→CaS₅+2H₂O  (2)

Volck points out that the advantages of the above reaction include: (1)only polysulfide is produced; (2) the reaction proceeds quickly atambient or warmer temperatures; (3) less sludge solids are produced; and(4) higher concentrations of polysulfide can be achieved. A relatedmethod for making calcium polysulfide using lime and hydrogen sulfidewas subsequently developed and disclosed in U.S. Pat. No. 2,135,879 toShiffler et al.

Many of the methods for making sodium polysulfide were developedspecifically for applications in the pulp and paper industry wherealkaline polysulfide cooking liquors are used to digest wood. U.S. Pat.No. 3,216,887 to Landmark and U.S. Pat. No. 4,024,229 to Smith et al.disclose oxygenation of sodium sulfide to form sodium polysulfide andsodium thiosulfate. U.S. Pat. No. 5,234,546 to Chamblee discloses avariety of techniques for recovering sodium polysulfide from variouscooking liquors using techniques such as fuel cells and activated carboncatalyzed oxidation reactions. U.S. Pat. No. 6,264,819 to Andoh et al.discloses an electrolytic oxidation method for producing a sodiumpolysulfide cooking liquor which involves electrolytically oxidizingpulping liquors. Such applications are generally limited to relativedilute solutions of sodium polysulfide, e.g., typically in the range of0.5% to 8.0%. Moreover they generally produce, or are susceptible toproducing, thiosulfate along with the polysulfide.

DISCLOSURE OF THE INVENTION

According to various features, characteristics and embodiments of thepresent invention which will become apparent as the description thereofproceeds, the present invention provides a calcium-sodium polysulfidechemical reagent containing calcium polysulfide and sodium polysulfidein molar ratios ranging from about 9:1 to 1:9 and, according to oneembodiment in a molar ratio of about 1:1.

The calcium-sodium polysulfide chemical reagent is a reaction productproduced by reacting a source of alkalinity, a source of elementalsulfur, and a source of sulfide ions together. The source of alkalinitycomprises at least one of hydrated lime, quick lime, sodium hydroxideand potassium hydroxide. The source of elemental sulfur comprises atleast one of virgin sulfur or waste sulfur. The source of sulfide ionscomprises at least one of sodium hydrosulfide, sodium sulfide, calciumhydrosulfide and hydrogen sulfide.

The present invention further provides a component polysulfide reagentcontaining calcium polysulfide and sodium polysulfide and at least oneof potassium polysulfide and aluminum polysulfide wherein at least twoof the polysulfides each comprise at least 10 wt. % of the totalpolysulfide content.

The present invention also provides a method for making a polysulfidereagent which involves:

providing a source of alkalinity;

providing a source of elemental sulfur;

providing a source of sulfide ions;

providing a reactor vessel; and

reacting the source of alkalinity, the source of elemental sulfur andthe source of sulfide ions together in the reactor vessel.

According to one embodiment the source of alkalinity and the source ofelemental sulfur are premixed together before being combined with thesource of sulfide ions. Moreover, the source of alkalinity and thesource of elemental sulfur can be premixed before being placed into thereactor vessel. The reaction can be carried out at room temperature orat a temperature above room temperature.

The present invention also provides a method of stabilizing oxyanions ofchrome which involves:

providing a waste material that includes an oxyanion of chrome;

providing a polysulfide reagent containing calcium polysulfide andsodium polysulfide; and

applying the polysulfide reagent to the waste material to stabilize theoxyanion of chrome against excessive leaching.

According to one embodiment the waste material to be treated orstabilized comprises chromite ore processing residue.

BRIEF DESCRIPTION OF DRAWINGS

The present invention will be described with reference to the attacheddrawings which are given as non-limiting examples only, in which:

FIG. 1 is a flowchart depicting one manner of combining reagents to makea calcium-sodium polysulfide reagent according to one embodiment of thepresent invention.

FIG. 2 is a flowchart depicting another manner of combining reagents tomake a calcium-sodium polysulfide reagent according to anotherembodiment of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is directed to polysulfide chemical reagents,methods for producing the reagents and methods of using the reagents.The polysulfide chemical reagents of the present invention are blends ofsulfides that can be prepared from a variety of reactant sources. Forexample, the polysulfide chemical reagents of the present invention canbe a blend of calcium polysulfide and sodium polysulfide that isprepared using various types, sources and ratios of lime, elementalsulfur and sulfide ion using either virgin or waste materials. Thepolysulfide reagents of the present invention are amenable toinexpensive and high rate production methods at ambient or warmertemperatures. Reference herein to “virgin sulfur” or “virgin reagents”or “virgin reactants” is intended to contrast between sulfur, reagents,and reactants that are derived from the direct or indirect use of wastesources and waste materials that include the sulfur, reagents, andreactants, i.e. “waste sources” (including “waste sulfur”). In practice,the use of waste sources and waste materials that contain or include thesulfur, reagents and reactants can reduce costs and provide a way ofrecovering some value from the waste sources and waste materials.However, it is to be understood that, as opposed to waste sources andwaste materials, the sulfur, reagents and reactants can comprise anycommercially available sources of these materials which is referred toherein as “virgin” sources.

The polysulfide reagent can be used to precipitate metals fromwastewater, stabilize multivalent metals such as chrome in hazardouswaste residues, remove mercury from flue gases, and as an electrolyte inlarge-scale bromide/polysulfide electrical storage batteries.

As disclosed in co-pending U.S. patent application Ser. No. 10/977,826,(to which priority of the present invention is claimed under 35 U.S.C.§120 and of which the entire specification is hereby expresslyincorporated by reference), calcium polysulfide or other polysulfidebearing materials can be added to the process developed to stabilizeselenium for the specific purpose of assisting in stabilizing otheroxyanions such as chrome by adjusting the oxidation-reduction potentialof the stabilized waste matrix. Accordingly, the inventors of thepresent invention recently discovered that polysulfide reagents areeffective in stabilizing oxyanions such as chrome based upon adjustmentof the oxidation-reduction potential of the reaction matrix.

During the course of the present invention the inventor determined thatin many applications such as waste water treatment, residuestabilization and air emissions abatement, etc., it is not importantwhether the polysulfide reagent used is calcium polysulfide, sodiumpolysulfide, or some other form of polysulfide such as potassiumpolysulfide. Rather, in such applications, it is more important that thepolysulfide reagent used is mainly polysulfide, and that it isrelatively concentrated. From an economical standpoint, it is desirablethat the polysulfide reagent is easy to produce in large quantities, andthat it can be produced using a variety of inexpensive raw materials orbyproduct wastes. The polysulfide chemical reagents of the presentinvention meet these desired criteria.

In contrast to making calcium polysulfide alone or sodium polysulfidealone, the present invention is directed to a chemical reagent thatcomprises a mixture of calcium polysulfide and sodium polysulfide thatis referred to herein as calcium-sodium polysulfide. The formulation ofthis reagent is based on the following generalized reaction:2NaHS+Ca(OH)₂+2(x−1)S^(o)═Na₂S_(x)+CaS_(x)+2H₂O  (3)Calcium-sodium polysulfide reagent formulations that strictly adhere tothis reaction result in a 1:1 molar ratio of sodium polysulfide andcalcium polysulfide, both of which are highly soluble. The ratio can beeasily varied, however, depending on the type of sulfide and alkalinematerials most readily available. For example, virgin or waste causticcan be substituted or partially substituted for the lime, and calciumhydrosulfide can be substituted or partially substituted for the sodiumhydrosulfide. If desired, the reagent can be prepared from virginmaterials such as 25% NASH or 45% NaSH, hydrated lime (Ca(OH)₂) or quicklime (CaO), and various types of elemental sulfur products.Alternatively, the calcium-sodium polysulfide reagent can be preparedusing waste materials such as variable percent NaSH solutions fromcaustic scrubbing of hydrogen sulfide gases, waste lime sludges orsolids from industrial production operations or air pollution controlequipment, and sulfur filter cake such as typically generated from gasdesulfurization processes using recirculated solutions of chelated iron.In some cases, the spent caustic solution from scrubbing of sulfidegases can have significant amounts of excess caustic in addition to theNaSH, thereby reducing the amount of other alkaline reagents needed tosatisfy the general stoichiometry of Eq. 3. As a practical matter, themolar ratio of calcium polysulfide to sodium polysulfide in thecalcium-sodium polysulfide reagent of the present invention can rangefrom 9:1 to 1:9.

The calcium-sodium polysulfide reagents of the present invention can bemade from various types of the raw materials that may be, in someinstances, available as byproducts. Depending on the sources of rawmaterials the sodium or calcium can be replaced by other cations such aspotassium or aluminum.

The polysulfide reagents of the present invention are made by combining:(1) a source of alkalinity from any of a variety of sources such ashydrated lime, quick lime, sodium hydroxide and potassium hydroxide; (2)elemental sulfur from any of a variety of sources such as virgin sulfurprills or waste sulfur filter cake; and (3) a source of sulfide ionsfrom any of a variety of sources such as sodium hydrosulfide, sodiumsulfide, calcium hydrosulfide and hydrogen sulfide.

In general, these reactants are added in accordance with thestoichiometry shown in Eq. 3 or in amounts that will produces a desiredratio of the individual polysulfides.

FIG. 1 is a flowchart depicting one manner of combining reagents to makea calcium-sodium polysulfide reagent according to one embodiment of thepresent invention. As shown in FIG. 1, the reactants can all be added toa single reactor 1. Typically a source of alkalinity 5 from any of avariety of sources such as hydrated lime, quick lime, sodium hydroxideand potassium hydroxide and a source of elemental sulfur 4 from any of avariety of sources such as virgin sulfur prills or waste sulfur filtercake are added into the reactor 1 together with any supplemental water 6used to dissolve the reactants (which can be added in aqueous forms).The reactor 1 can then optionally be heated, for example, by steaminjection or any other suitable heating means. Thereafter the source ofsulfide ions 7 from any of a variety of sources such as sodiumhydrosulfide, sodium sulfide, calcium hydrosulfide and hydrogen sulfidecan be added to the reactor 1. Depending on the sources of thereactants, heating of the reactor may not be required as the reactionwill take place at room temperature. After the reaction is complete theresulting reaction products can be subject to a separation process 2 inwhich solids are removed from the calcium-sodium polysulfide reagentproduct. Any suitable solids separation process or equipment can beutilized.

FIG. 2 is a flowchart depicting another manner of combining reagents tomake a calcium-sodium polysulfide reagent according to anotherembodiment of the present invention. As shown in FIG. 2, the source ofalkalinity 5 and source of elemental sulfur 4 can be pre-mixed in anintermediate vessel 3 to provide a slurry that is thereafter transferredto a reactor 1 into which the sulfide source 7 is added. As in the caseof the reaction flowchart of FIG. 1, the reactor 1 can then optionallybe heated, for example by steam injection or any other suitable heatingmeans before or after the source of sulfide ions is added to the reactor1. Also, depending on the sources of the reactants, heating of thereactor 1 may not be required as the reaction will take place at roomtemperature. In addition, as in the case of the reaction flowchart ofFIG. 1, after the reaction is complete, the resulting reaction productscan be subject to a separation process 2 in which solids are removedfrom the calcium-sodium polysulfide reagent product. Any suitable solidsseparation process or equipment can be utilized. It is noted that thesource of alkalinity 5 and source of elemental sulfur 4 can be pre-mixedin the reactor 1 rather than in a separate intermediate vessel.

The reaction schemes of both flowcharts in FIGS. 1 and 2 are amenable tobatchwise, semi-batchwise or continuous production methods. Depending onthe end use of the polysulfide reagent, removal of suspended solids maybe performed, if needed, using any of a variety of processes, techniquesand equipment such as gravity settling or filtration. In general, thereactions can be performed at room temperature but operation at about125° F. to 150° F. accelerates reaction rate considerably.

The ability to premix the source of alkalinity and elemental sulfur withwater to form a pumpable slurry, before transferring the premixed slurryinto a reactor (where the sulfide reagent is added) allows the method tobe used easily with waste sources of lime sludges and sulfur filtercakes that would be difficult to transfer into a closed reactor. Becauseno reaction takes place at room temperature when the source ofalkalinity (waste lime) and elemental sulfur (waste sulfur) arecombined, these two reactants can be readily mixed with water inopen-topped basins and then pumped to a reactor where the sulfidereagent is then added.

Features and characteristics of the present invention will beexemplified by the following examples which are provided as non-limitingexamples only. In the examples and throughout percentages are by weightunless otherwise indicated or determined by context.

Example 1

In this example, a calcium-sodium polysulfide reagent was produced bycombining the raw materials to a single mixing tank or reactor in themanner illustrated in FIG. 1. More specifically, a full-scale test wasperformed to verify that the method was simple and rapid. Thedemonstration produced about 3,500 gallons of calcium-sodium polysulfidereagent having a specific gravity of 1.31 and a total sulfur content ofabout 27%. The production method involved adding about 1,150 gallons ofwater (including some steam condensate) to an enclosed reactor with amixing device and then adding 3,000 lbs of calcium hydroxide. 18,160 lbsof 25% NASH solution was also added to the reactor. Live steam wasbriefly injected into the reactor to raise the temperature to 150° F.Next, approximately 7,840 lbs of elemental sulfur prills were added tothe reactor and within less than an hour of mixing, the reaction wascomplete. The resultant product was deep red in color and had a specificgravity of 1.31 and a total sulfur content of 27%.

Example 2

In this example, the calcium-sodium polysulfide reagent produced inExample 1 was tested for its ability to stabilize chromite oreprocessing residue (COPR) containing high levels of chrome. Theapplicability of the calcium-sodium polysulfide reagent to stabilizechrome residues was verified by applying various doses of thecalcium-sodium polysulfide reagent to three different samples ofchromite ore processing residue (COPR). The three samples used in thisexperiment had the following total chrome contents: COPR-1=1.8% Cr,COPR-3=2.4% Cr and COPR-4 of 1.3%. In accordance with EnvironmentalProtection Agency (EPA) requirements for this type of waste material,the concentration of chrome in the leachate from the TCLP (toxicitycharacteristic leachate procedure) test protocol must be less than 0.60mg/L after stabilization. The untreated TCLP leachate chromeconcentrations for the three samples ranged from 40 mg/L to 100 mg/L.The results of the tests which included treating the COPR samples withdifferent dosages (based upon percent by volume of the calcium-sodiumpolysulfide reagent) are summarized in Table I below.

TABLE I Liquid TCLP Cr for TCLP Cr TCLP Cr for Reagent Dose COPR-1 forCOPR-3 COPR-4 (% by weight) (mg/L) (mg/L) (mg/L)  5.0% 1.85 7.56 10.72 7.5% 0.28 0.05 0.16 10.0% 0.01 0.15 <0.01 12.5% <0.01 0.02 <0.01 15.0%<0.01 0.02 <0.01 20.0% <0.01 <0.01 <0.01

From the date in Table I, it can be seen that a 7.5% liquid dose orhigher of the calcium-sodium polysulfide reagent stabilized the chromein all three of the COPR samples to well below the 0.60 mg/L TCLPcriterion.

Example 3

In this example, a calcium-sodium polysulfide reagent was produced bycombining the raw materials to a single mixing tank or reactor in themanner illustrated in FIG. 2. More specifically, a bench-scale test wasconducted in which 74.5 grams of a sulfur filter cake (containing about75% sulfur) was placed into 36 mL of tap water and stirred. 43.2 gramsof lime filter cake (about 50% solids) was then added to the mixture andthe resulting mixture was mixed to form a pumpable slurry. The slurrywas transferred into a beaker to which 54.6 mL of 45% NaSH was thenadded and then an additional 39 mL of tap water was added. Within a fewminutes after stirring at room temperature the slurry had completelyreacted producing a deep-red calcium-sodium polysulfide alkalinereagent. The reagent had a specific gravity of 1.32 and a total sulfurcontent of 24.6%.

Example 4

In this example, the calcium-sodium polysulfide reagent produced inExample 1 was tested for its ability to stabilize chromite oreprocessing residue (COPR) containing high levels of chrome. Theparticular sample of the COPR was the same as sample COPR-1 listed inTable I above. This sample had a total chrome content of 1.8% and anuntreated TCLP leachate concentration of 40 mg/L. The results of thetests which included treating the COPR sample with different dosages(based upon percent by volume of the calcium-sodium polysulfide reagent)are summarized in Table II below

TABLE II TCLP Cr TCLP Cr Liquid after 0 days after 9 days Reagent Dosecure time cure time (% by weight) (mg/L) (mg/L)  6% 1.48 —  8% 0.28 —10% 0.04 0.03 15% 0.05 0.06

From the data in Table II, it can be seen that an 8% liquid dose orhigher of the calcium-sodium polysulfide reagent stabilized the chromein the COPR sample. It is noted that for this series of tests, TCLPtests were performed immediately after the reagent doses were added, andTCLP tests were repeated after nine days of sample curing. The TCLP testresults were essentially the same for zero days and nine days of curetime, thereby indicating immediate and effective stabilization.

Example 5

In this example, a series of test formulations was conducted todemonstrate that the calcium-sodium polysulfide reagent of the presentinvention can be made relatively concentrated compared to currentcommercial grades of calcium polysulfide. One of the formulations used15 grams lime, 40 grams sulfur and 80 mL of 25% sodium hydrosulfide(NaSH) with no water addition. The reaction was relatively fast andresulted in a calcium-sodium polysulfide solution with a specificgravity of 1.43 and a total sulfur content of about 37%. This iscompared to commercial calcium polysulfide that has a specific gravityof about 1.27 and a total sulfur content of about 23%.

The results from the above examples demonstrated the effectiveness ofthe calcium-sodium polysulfide reagent and the ability to easily producethe reagent in a variety of ways using a variety of raw materials over arange of concentrations at ambient or warmer temperatures.

Although the present invention has been described with reference toparticular means, materials and embodiments, from the foregoingdescription, one skilled in the art can easily ascertain the essentialcharacteristics of the present invention and various changes andmodifications can be made to adapt the various uses and characteristicswithout departing from the spirit and scope of the present invention asdescribed above and in the claims that are attached hereto.

1. A method for making a polysulfide reagent which comprises: providinga source of alkalinity; providing a source of elemental sulfur;providing a source of sulfide ions selected from the group consisting ofsodium hydrosulfide, sodium sulfide, calcium hydrosulfide and mixturesthereof; providing a reactor vessel; and reacting the source ofalkalinity, the source of elemental sulfur and the source of sulfideions together in the reactor vessel.
 2. A method for making apolysulfide reagent according to claim 1, wherein the source ofalkalinity comprises a member selected from the group consisting ofhydrated lime, quick lime, sodium hydroxide, potassium hydroxide andmixtures thereof.
 3. A method for making a polysulfide reagent accordingto claim 1, wherein the source of elemental sulfur comprises a memberselected from the group consisting of virgin sulfur, and waste sulfurand mixtures thereof.
 4. A method for making a polysulfide reagentaccording to claim 1, wherein the source of alkalinity and the source ofelemental sulfur are premixed together before being combined with thesource of sulfide ions.
 5. A method for making a polysulfide reagentaccording to claim 4, wherein the source of alkalinity and the source ofelemental sulfur are premixed before being placed into the reactorvessel.
 6. A method for making a polysulfide reagent according to claim1, wherein the reaction is carried out at room temperature.
 7. A methodfor making a polysulfide reagent according to claim 1, wherein thereaction is carried out at a temperature above room temperature.
 8. Amethod for making a polysulfide reagent according to claim 1, whereinthe polysulfide reagent comprises calcium-sodium polysulfide.
 9. Amethod for making a polysulfide reagent according to claim 1, whereinthe polysulfide reagent comprises a calcium polysulfide, and a memberselected from the group consisting of potassium polysulfide, aluminumpolysulfide and mixtures thereof wherein at least two of thepolysulfides each comprise at least 10 wt. % of the total polysulfidecontent.
 10. A method for making a polysulfide reagent according toclaim 1, wherein the polysulfide reagent comprises sodium polysulfide,and a member selected from the group consisting of potassiumpolysulfide, aluminum polysulfide and mixtures thereof wherein at leasttwo of the polysulfides each comprise at least 10 wt. % of the totalpolysulfide content.